CN105155033B - A kind of composite fibre of Flameproof polyamide 6 and preparation method thereof - Google Patents
A kind of composite fibre of Flameproof polyamide 6 and preparation method thereof Download PDFInfo
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- CN105155033B CN105155033B CN201510435314.9A CN201510435314A CN105155033B CN 105155033 B CN105155033 B CN 105155033B CN 201510435314 A CN201510435314 A CN 201510435314A CN 105155033 B CN105155033 B CN 105155033B
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Abstract
The present invention relates to a kind of composite fibre of Flameproof polyamide 6 and preparation method thereof, more particularly to a kind of phosphorous reactive flame retardant, react to obtain block copolymerization Flameproof polyamide 6 by the continuous two-stage polymerization to carry out respectively, and the method for the composite fibre of Flameproof polyamide 6 is obtained with fibre-forming polymer melt composite spinning.It is characterized in that fire retardant obtains fire retardant performed polymer with diamine or diol reaction first, then fire retardant performed polymer is copolymerized to obtain the material of Flameproof polyamide 6 again with the prepolymer reaction of polyamide 6, after Cast Strip pelletizing, extraction are dried, the composite fibre of Flameproof polyamide 6 is obtained with fibre-forming polymer section melt composite spinning first break draft.The composite fibre of Flameproof polyamide 6 that this method obtains has the characteristics of fire retardant addition is few, flame retardant effect is lasting, feel is fluffy comfortable, textile article can be made, be mainly used in knitting wool, woollen blanket, wool fabric, warming wadding suede inserts, silk fabric, non-woven cloth, medical and hygiene article and particular job clothes etc..
Description
Technical field
The invention belongs to Flameproof polyamide fiber synthesis technical field, is related to a kind of composite fibre of Flameproof polyamide 6 and its system
Preparation Method, contain fire retardant by continuous and what the two-stage polymerization that carries out respectively reacted to obtain block copolymerization more particularly to a kind of
Composite fibre of Flameproof polyamide 6 of performed polymer and preparation method thereof.
Background technology
Fypro is referred to as polyamide fibre in China, abroad also known as nylon, nylon, capron etc..As synthetic fibers
Earliest industrialized kind, daiamid-6 fiber is with its excellent intensity, wearability, hygroscopicity, resilience, in civilian and industry
Very important effect has been played with field.But the limited oxygen index of daiamid-6 fiber only has 21% or so, belong to flammable fibre
Dimension, the research to the composite fibre of Flameproof polyamide 6 turn into a problem in the urgent need to address.
The flame resistant method of Fypro or textile is roughly divided into that precursor is flame-retardant modified and the major class of flame-retardant after-finishing two.
Finishing method is applied widely, and technique is simple, but can influence the feel of fabric, and weightening is larger and not washable, is mainly used in window
The flame retardant treatment of the fabrics such as curtain, curtain.Precursor is flame-retardant modified and is divided into blending and modifying and modification by copolymerization, co-mix-modified flame-retardant fiber
It is that additive flame retardant is added into spinning after blending, fire retardant in polyamide section not enter among molecular structure but with gathering
Compound uniformly mixes, have it is easy to use, it is widely applicable the characteristics of, but easily separated out there is fire retardant, flame retardant effect is not held
Problem long and influential on mechanical performance.Modification by copolymerization fire resistance fibre is that being total to anti-flammability is added in synthesizing polyamides
Polycondensation monomer, so that fire-resistant copolyesters monomer is aggregated among polyamide macromolecular fire-retardant effect of playing, but modification by copolymerization face
Face the problems such as reactive flame retardant species is few, processing technology is complicated, used currently without additive flame retardant universal.
For Fypro, flame-retardant modified copolymerization is its flame-retardant modified important way, is hindered by using response type
Combustion agent polyamide is carried out it is flame-retardant modified polyamide is obtained excellent fire resistance, and reactive flame retardant with
The form of chemical bond is bonded on the molecular backbone of polyamide, can thus be overcome fire-retardant caused by other flame-retardant modified modes
The shortcomings of agent easily separates out, flame retardant effect is not lasting, big to Effect on Mechanical Properties.2- carboxylic second is used in patented technology CN1267475C
The monomer copolymerization of base phenyl phosphinic acid (CEPPA) and polyamide 66 obtains the polymer of Flameproof polyamide 66, and fire retardant CEPPA is combined
Onto the molecular backbone of polyamide 66, the fiber of Flameproof polyamide 66 is obtained.It is generally common but copolymerization is flame-retardant modified there is also shortcoming
It is that the monomer direct polymerization of fire retardant and polyamide is obtained into the random copolymer of polyamide and fire retardant to gather flame-retardant modified, fire-retardant
Agent is random distribution in polyamide, for random copolymer, with the increase of noncrystalline comonomer (fire retardant) content, is melted
Point monotony declines, and we are also required to simultaneously facing to both needing a certain amount of fire retardant to obtain the fiber of Flameproof polyamide 6 with modification
The contradiction of the resistant to elevated temperatures performance of daiamid-6 fiber is maintained, which limits the use of daiamid-6 fiber.
Composite spinning is by the melt or concentrated solution of two or more fiber-forming polymer, utilizes component, proportioning, viscosity
Or the difference of kind, while by a spinning head with particular allocation system, sprayed in same spinneret orifice and turn into one
Root fiber, and mutually accumulate fibre section shape set in advance.Composite spinning turns into become more and more important and generally uses
Fibrous physics modification technology, composite fibre has 3 D stereo curling, high fluffy and the characteristics of spreadability, utilizes Compound spinning
Silk can be made with flame-retardant modified specific function fiber, be mainly used in knitting wool, woollen blanket, wool fabric, warming wadding suede inserts,
Non-woven cloth, medical and hygiene article and particular job clothes etc..
The content of the invention
It is an object of the invention to provide a kind of composite fibre of Flameproof polyamide 6 and preparation method thereof, more particularly to one kind
The Flameproof polyamide 6 containing fire retardant performed polymer for reacting to obtain block copolymerization respectively by the two-stage polymerization continuously to carry out is multiple
Condensating fiber and preparation method thereof.The present invention reacts to obtain the fire-retardant polyamides of block copolymerization by the continuous two-stage polymerization to carry out respectively
The material of amine 6, the Flameproof polyamide 6 obtained after Cast Strip pelletizing, extraction drying, with fibre-forming polymer melt composite spinning and drawing-off
Composite fibre.Hardly change the fusing point of daiamid-6 fiber while its fire resistance is improved, maintaining its resistant to elevated temperatures makes
With performance, because for block copolymer, when comonomer (fire retardant) content increases to very big, fusing point remains in that not
Become.It is compound with common polyamide 6 meanwhile block copolymer overcomes random copolymerization and material crystal structure is destroyed the shortcomings that big
Fiber is compared, and the fusing point and crystal property of the composite fibre of Flameproof polyamide 6 have no significant change, and it is processed and mechanical property does not have yet
There is big change.By the composite fibre boiling water treating 48h of Flameproof polyamide 6 of the present invention, its mechanical property and fire resistance with not
Compare and have almost no change before boiling water treating.Therefore, the Flameproof polyamide 6 with block copolymeric structure that the present invention obtains is compound
Fiber can be made with flame-retardant modified specific function fiber, be mainly used in knitting wool, woollen blanket, wool fabric, warming wadding suede filling
Material, non-woven cloth, medical and hygiene article and particular job clothes etc..
A kind of composite fibre of Flameproof polyamide 6 of the present invention, it melts Compound spinning by Flameproof polyamide 6 and fibre-forming polymer
Silk forms, and the molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X >=50, y >=50, for the number of repeat unit of polyamide 6；
Z >=2, it is the number of repeat unit of fire retardant；
And 1/100≤z/ (x+y)≤1/10；
R is
The R1、R3For straight chain, branched or ring-type C1~C15Alkylidene；R2、R4For straight chain, branched or ring-type C1~
C15Alkyl or aryl；R5、R6For the C of straight chain1~C15Alkylidene.
As preferable technical scheme：
A kind of composite fibre of Flameproof polyamide 6 as described above, the limited oxygen index of the composite fibre of Flameproof polyamide 6
More than 30%；The fracture strength of the composite fibre of Flameproof polyamide 6 is 4.0~6.7cN/dtex, elongation at break 22~
38%, Young's modulus is 20~37cN/dtex.
Present invention also offers a kind of preparation method of the composite fibre of Flameproof polyamide 6, first by fire retardant and diamine
Or dihydric alcohol polycondensation obtains fire retardant performed polymer, then fire retardant performed polymer and the polyamide 6 performed polymer after pre-polymerization are occurred
Copolyreaction, the material of Flameproof polyamide 6 is obtained, through Cast Strip pelletizing, extraction drying, be added to the section of other fibre-forming polymers molten
Melt compined spinning apparatus and carry out melt composite spinning, drawing-off, obtain the composite fibre of Flameproof polyamide 6；The fire retardant performed polymer
For viscous liquid or semisolid, number-average molecular weight Mn is 103~104, and molecule both ends be with carboxyl, amido or
The active function groups of hydroxyl；
The structure of the fire retardant is：
The R1、R3For straight chain, branched or ring-type C1~C15Alkylidene；R2、R4For straight chain, branched or ring-type C1~
C15Alkyl or aryl.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, the formula of the diamine is H2N-R5-
NH2, the formula of dihydric alcohol is HO-R6-OH；R5、R6For the C of straight chain1~C15Alkylidene.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, specifically includes following steps：
(1) fire retardant, diamine or dihydric alcohol are mixed with water, it is well mixed at 50~80 DEG C under nitrogen protection, then
The stirring reaction at 90~130 DEG C, then 150~180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates life
Into fire retardant performed polymer；The mol ratio of the fire retardant, diamine or dihydric alcohol and water is 1:0.8~1.5:2~2.5, gained
The both ends of fire retardant performed polymer are the active function groups with carboxyl, amido or hydroxyl；
(2) 88~96 mass parts caprolactams, 0.5~5 mass parts water and 0.1~1 mass parts adipic acid are added and reacted
Kettle, stir and be warming up to 245 DEG C~250 DEG C, when pressure reaches 0.5MPa~0.9MPa, heat-insulation pressure keeping reaction a period of time,
Then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer is 103~104, and
The both ends of polyamide 6 performed polymer are respectively the active end group of a carboxyl and amido, and such polyamide 6 performed polymer and fire retardant are pre-
The active end group that can be reacted to each other just is provided between aggressiveness；
(3) fire retardant performed polymer described in 0.5~10 mass parts is added in the polyamide 6 performed polymer, opens stirring and turn
Speed is 200~400r/min, is warming up to 235 DEG C~240 DEG C, 6~8h of copolyreaction, makes fire retardant performed polymer and polyamide 6 pre-
Aggressiveness is copolymerized, and fire retardant performed polymer can be uniformly dispersed in polyamide 6 performed polymer under high velocity agitation, between two performed polymers
Active end group between can react to each other, strand gradually increases；
(4) then, -0.05~-0.1MPa is evacuated down to, stops stirring after being kept for a period of time, after standing 10~20min
Logical nitrogen discharging, gained reaction product obtain Flameproof polyamide 6 and cut into slices, due to that can be produced in course of reaction less through Cast Strip pelletizing
The moisture of amount, suppresses the growth of strand, now vacuumizes removing excessive moisture so that the molecular weight of polymer further increases
Add.
(5) Flameproof polyamide 6 is cut into slices extraction, dry a period of time, certain mass is pressed with the section of other fibre-forming polymers
Melt composite spinning, drawing-off are carried out than being added to compined spinning apparatus, that is, obtains the composite fibre of Flameproof polyamide 6.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, in step (1), 2~3h is well mixed,
2~3h of stirring reaction, further it polymerize 2~3h；In step (2), stir and heat up, rotating speed is 200~400r/min；Insulation is protected
Pressure reaction a period of time, refer to that heat-insulation pressure keeping reacts 2~4h；In step (4), kept for a period of time refer to 0.5~1h of holding.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, step (2) is middle to be stirred and is needed before heating up
First it is passed through N2Air in kettle is discharged, needs to lead to N into kettle when fire retardant performed polymer is added in reactor in step (3)2Protection resistance
Fire agent performed polymer and polyamide 6 performed polymer is not oxidized.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, Flameproof polyamide 6 is cut into slices in step (5)
Extraction refer to extract 24~48h at 95~100 DEG C, the drying of section refer at 90~110 DEG C vacuum drying 12~
48h。
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, Flameproof polyamide 6 is cut into slices in step (5)
Melt composite spinning temperature be 265~285 DEG C, drafting multiple be 3.2~3.8；Flameproof polyamide 6 is cut into slices and fibre-forming polymer
The mass ratio of section is 1:0.8~1.2.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, the fibre-forming polymer are polyamide, gathered
Ester or polypropylene.
A kind of preparation method of the composite fibre of Flameproof polyamide 6 as described above, the Flameproof polyamide obtained in step (5)
6 composite fibres are parallel type, core-skin type, exfoliated or fabric of island-in-sea type.
Beneficial effect：
1st, the present invention is developed fire-retardant poly- by the way that the performed polymer of reactive flame retardant is attached on the main chain of polyamide 6
The composite fibre of acid amides 6, have fire retardant addition is few, good flame retardation effect and persistently, it is small to Effect on Mechanical Properties the advantages of.
2nd, the present invention reacts to obtain the composite fibre of Flameproof polyamide 6 by the continuous two-stage polymerization to carry out respectively, is carrying
While 6 flame-retardant fiber of super polyamide, its fusing point is almost unchanged, maintains its resistant to elevated temperatures performance.
3rd, fabric and product made of the obtained composite fibre of Flameproof polyamide 6 of the present invention have good feel and water-fast
Washing property, available for knitting wool, woollen blanket, wool fabric, warming wadding suede inserts, non-woven cloth, medical and hygiene article and particular job clothes
Deng.
Brief description of the drawings
Fig. 1 is the structural representation of compined spinning apparatus in the present invention；
Fig. 2 is the schematic cross-section of the composite fibre of parallel type Flameproof polyamide 6 in the present invention；
Fig. 3 is the schematic cross-section of the composite fibre of core-skin type Flameproof polyamide 6 in the present invention；
Fig. 4 is the schematic cross-section of the exfoliated composite fibre of Flameproof polyamide 6 in the present invention；
Fig. 5 is the schematic cross-section of the composite fibre of fabric of island-in-sea type Flameproof polyamide 6 in the present invention.
In Fig. 1：
1- Flameproof polyamides 6 are cut into slices；The other fibre-forming polymer sections of 2-；3- screw extruders；
4- measuring pumps；5- composite spining modules；The composite fibre of 6- Flameproof polyamides 6
Embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant DDP, hexamethylene diamine are mixed with water, in 50 DEG C of well mixed 2h under nitrogen protection, then at 90 DEG C
Stirring reaction 2h, then 150 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant performed polymer, its
For viscous liquid, number-average molecular weight Mn is 1.8 × 103, fire retardant DDP, hexamethylene diamine and water mol ratio are 1:1.1:2, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively carboxyl and amido；
The structure of fire retardant is：
(2) 90.7 mass parts caprolactams, 4.0 mass parts water and 0.3 mass parts adipic acid are added into reactor, are first passed through
N2Air in kettle is discharged, is stirred using rotating speed as 200r/min and is warming up to 245 DEG C, when pressure reaches 0.5MPa, heat-insulation pressure keeping
React 2h, then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer 6.0 ×
103, and be respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and resistance
The active end group that can be reacted to each other just is provided between combustion agent performed polymer；
(3) 5.0 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 200r/min, are warming up to 235 DEG C, copolyreaction 6h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.05MPa is evacuated down to, stops stirring after keeping 0.5h, leads to nitrogen discharging, institute after standing 10min
Reaction product is obtained through Cast Strip pelletizing, Flameproof polyamide 6 is obtained and cuts into slices；
(5) Flameproof polyamide 6 is cut into slices 100 DEG C after extracting 48h, 100 DEG C of vacuum drying 24h, matter is pressed with polyamide 6 section
Measure ratio 1:1 is added to side. by-side conjugation spinning device (as shown in Figure 1) carries out melt composite spinning at 275 DEG C, and drafting multiple is
3.5 times, the section of Flameproof polyamide 6 and polyamide 6 section pass sequentially through after screw extruder, measuring pump through composite spinning group respectively
Part obtains the composite fibre of parallel type Flameproof polyamide 6 (as shown in Figure 2).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=126, it is the number of repeat unit of polyamide 6；Z=4, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 34.2%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 5.30cN/dtex, elongation at break 31.37%, Young's modulus 31cN/dtex.
Embodiment 2
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant CEPPA, hexamethylene diamine are mixed with water, in 80 DEG C of well mixed 3h under nitrogen protection, then 130
Stirring reaction 3h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is semisolid, and number-average molecular weight Mn is 2.5 × 103, fire retardant CEPPA, hexamethylene diamine and water mol ratio are 1:1.2:
2.5, obtained flame-retardant agent performed polymer both ends are respectively the active end group of carboxyl and amido；
The structure of fire retardant is：
(2) 88.5 mass parts caprolactams, 1.5 mass parts water and 0.5 mass parts adipic acid are added into reactor, are first passed through
N2Air in kettle is discharged, is stirred using rotating speed as 400r/min and is warming up to 250 DEG C, when pressure reaches 0.9MPa, heat-insulation pressure keeping
React 4h, then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer 6.5 ×
103, and be respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and resistance
The active end group that can be reacted to each other just is provided between combustion agent performed polymer；
(3) 9.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 400r/min, are warming up to 240 DEG C, copolyreaction 8h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.1MPa is evacuated down to, stops stirring after keeping 1h, leads to nitrogen discharging after standing 20min, gained is anti-
Product is answered to obtain Flameproof polyamide 6 through Cast Strip pelletizing and cut into slices；
(5) Flameproof polyamide 6 is cut into slices 98 DEG C after extracting 24h, 105 DEG C of vacuum drying 12h, with polyester slice in mass ratio
1:0.9, which is added to core-skin type compined spinning apparatus, carries out melt composite spinning at 275 DEG C, and drafting multiple is 3.5 times, fire-retardant polyamides
The section of amine 6 and polyester slice obtain core-skin type resistance through composite spining module after passing sequentially through screw extruder, measuring pump respectively
The composite fibre of retardant polyamide 6 (as shown in Figure 3).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=190, it is the number of repeat unit of polyamide 6；Z=8, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 33.5%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 5.35cN/dtex, elongation at break 25.41%, Young's modulus 24.66cN/dtex.
Embodiment 3
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant BCPPO, hexamethylene diamine are mixed with water, in 60 DEG C of well mixed 2.5h under nitrogen protection, then 95
Stirring reaction 2h at DEG C, then 160 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.8 × 103, fire retardant BCPPO, hexamethylene diamine and water mol ratio are 1:
1.2:2.1, obtained flame-retardant agent performed polymer both ends are respectively the active end group of carboxyl and amido；
The structure of fire retardant is：
(2) 92.9 mass parts caprolactams, 0.8 mass parts water and 0.8 mass parts adipic acid are added into reactor, are first passed through
N2Air in kettle is discharged, is stirred using rotating speed as 300r/min and is warming up to 248 DEG C, when pressure reaches 0.6MPa, heat-insulation pressure keeping
React 2.5h, then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer 8.0 ×
103, and be respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and resistance
The active end group that can be reacted to each other just is provided between combustion agent performed polymer；
(3) 5.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 300r/min, are warming up to 236 DEG C, copolyreaction 7h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.08MPa is evacuated down to, stops stirring after keeping 0.8h, leads to nitrogen discharging, institute after standing 12min
Reaction product is obtained through Cast Strip pelletizing, Flameproof polyamide 6 is obtained and cuts into slices；
(5) Flameproof polyamide 6 is cut into slices 100 DEG C after extracting 24h, 110 DEG C of vacuum drying 20h, quality is pressed with polyester slice
Than 1:1.1, which are added to exfoliated compined spinning apparatus, carries out melt composite spinning at 280 DEG C, and drafting multiple is 3.6 times, fire-retardant poly-
Acid amides 6 is cut into slices and polyester slice pass sequentially through respectively obtained through composite spining module after screw extruder, measuring pump it is exfoliated
The composite fibre of Flameproof polyamide 6 (as shown in Figure 4).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=134, it is the number of repeat unit of polyamide 6；Z=6, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 34.8%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 5.51cN/dtex, elongation at break 32.41%, Young's modulus 30.21cN/dtex.
Embodiment 4
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant CEMPP, hexamethylene diamine are mixed with water, in 70 DEG C of well mixed 3h under nitrogen protection, then 100
Stirring reaction 2h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.5 × 103, fire retardant CEMPP, hexamethylene diamine and water mol ratio are 1:
1.2:2.1, obtained flame-retardant agent performed polymer both ends are respectively the active end group of a carboxyl and amido；
The structure of fire retardant is：
(2) 93 mass parts caprolactams, 1.2 mass parts water and 0.4 mass parts adipic acid are added into reactor, is first passed through N2
Air in kettle is discharged, is stirred using rotating speed as 300r/min and is warming up to 248 DEG C DEG C, when pressure reaches 0.6MPaMPa, insulation is protected
Pressure reaction 2.5h, then unloads and is depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer is 8.0
×103, and be respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and
The active end group that can be reacted to each other just is provided between fire retardant performed polymer；
(3) 4.6 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 300r/min, are warming up to 236 DEG C, copolyreaction 7h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.08MPa is evacuated down to, stops stirring after keeping 0.8h, leads to nitrogen discharging, institute after standing 12min
Reaction product is obtained through Cast Strip pelletizing, Flameproof polyamide 6 is obtained and cuts into slices.
(5) Flameproof polyamide 6 is cut into slices 100 DEG C after extracting 48h, 100 DEG C of vacuum drying 12h, matter is pressed with polyamide 6 section
Measure ratio 1:0.9, which is added to side. by-side conjugation spinning device, carries out melt composite spinning at 272 DEG C, and drafting multiple is 3.4 times, fire-retardant
Polyamide 6 section and polyamide 6 section obtain simultaneously after passing sequentially through screw extruder, measuring pump respectively through composite spining module
The composite fibre (as shown in Figure 2) of row type Flameproof polyamide 6.The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=164, it is the number of repeat unit of polyamide 6；Z=10, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 33.7%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 6.44cN/dtex, elongation at break 34.31%, Young's modulus 33.58cN/dtex.
Embodiment 5
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant DDP, butanediol are mixed with water, in 70 DEG C of well mixed 2h under nitrogen protection, then at 100 DEG C
Lower stirring reaction 2.5h, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is semisolid, and number-average molecular weight Mn is 1.7 × 103, fire retardant DDP, butanediol and water mol ratio are 1:1:2.2, institute
Obtain the active end group that fire retardant performed polymer both ends are respectively carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 91.3 mass parts caprolactams, 1.5 mass parts water and 0.7 mass parts adipic acid are added into reactor, are first passed through
N2Air in kettle is discharged, is stirred using rotating speed as 250r/min and is warming up to 248 DEG C, when pressure reaches 0.8MPa, heat-insulation pressure keeping
3h is reacted, then unloads and is depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer is 9 × 103,
And it is respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and fire retardant
The active end group that can be reacted to each other just is provided between performed polymer；
(3) 6.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 350r/min, are warming up to 240 DEG C, copolyreaction 6h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.1MPa is evacuated down to, stops stirring after keeping 1h, leads to nitrogen discharging after standing 15min, gained is anti-
Product is answered to obtain Flameproof polyamide 6 through Cast Strip pelletizing and cut into slices；
(5) Flameproof polyamide 6 is cut into slices 100 DEG C after extracting 28h, 105 DEG C of vacuum drying 20h, matter is pressed with polyamide 6 section
Measure ratio 1:1.2, which are added to core-skin type compined spinning apparatus, carries out melt composite spinning at 270 DEG C, and drafting multiple is 3.85 times, resistance
The section of retardant polyamide 6 and polyamide 6 section obtain after passing sequentially through screw extruder, measuring pump respectively through composite spining module
The composite fibre of core-skin type Flameproof polyamide 6 (as shown in Figure 3).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=162, it is the number of repeat unit of polyamide 6；Z=4, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 35.2%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 5.69cN/dtex, elongation at break 28.47%, Young's modulus 29.40cN/dtex.
Embodiment 6
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant CEPPA, butanediol are mixed with water, in 80 DEG C of well mixed 2h under nitrogen protection, then 120
Stirring reaction 2h at DEG C, then 165 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 2.0 × 103, fire retardant CEPPA, butanediol and water mol ratio are 1:
0.9:2.2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 88.5 mass parts caprolactams, 2 mass parts water and 0.8 mass parts adipic acid are added into reactor, is first passed through N2
Air in kettle is discharged, is stirred using rotating speed as 260r/min and is warming up to 245 DEG C, when pressure reaches 0.8MPa, heat-insulation pressure keeping is anti-
Answer 2.8h, then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer 5.8 ×
103, and be respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and resistance
The active end group that can be reacted to each other just is provided between combustion agent performed polymer；
(3) 8.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 260r/min, is warming up to 235 DEG C, copolyreaction
6.5h, fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can uniformly disperse under high velocity agitation
In polyamide 6 performed polymer, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.05MPa is evacuated down to, stops stirring after keeping 1h, leads to nitrogen discharging, gained after standing 18min
Reaction product obtains Flameproof polyamide 6 and cut into slices through Cast Strip pelletizing；
(5) Flameproof polyamide 6 is cut into slices 98 DEG C after extracting 30h, 90 DEG C of vacuum drying 48h, quality is pressed with polypropylene chip
Than 1:0.8, which is added to sea-island-type composite spun device, carries out melt composite spinning at 275 DEG C, and drafting multiple is 3.2 times, fire-retardant poly-
Acid amides 6 is cut into slices and polypropylene chip passes sequentially through obtain island through composite spining module after screw extruder, measuring pump respectively
The composite fibre of type Flameproof polyamide 6 (as shown in Figure 5).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=177, it is the number of repeat unit of polyamide 6；Z=7, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 37.2%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 4.81cN/dtex, elongation at break 25.27%, Young's modulus 27.64cN/dtex.
Embodiment 7
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant BCPPO, butanediol are mixed with water, in 70 DEG C of well mixed 2h under nitrogen protection, then 130
Stirring reaction 2h at DEG C, then 180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 1.6 × 103, fire retardant BCPPO, butanediol and water mol ratio are 1:
1.1:2.3, obtained flame-retardant agent performed polymer both ends are respectively the active end group of carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 90 mass parts caprolactams, 5 mass parts water and 1 mass parts adipic acid are added into reactor, is first passed through N2Discharge
Air in kettle, stirred using rotating speed as 210~r/min and be warming up to 245 DEG C, when pressure reaches 0.5MPa, heat-insulation pressure keeping reaction
4h, then unload and be depressed into normal pressure, obtain polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer is 6.8 × 103, and
And at the both ends of polyamide 6 performed polymer be respectively the active end group of carboxyl and amido, such polyamide 6 performed polymer and fire retardant are pre-
The active end group that can be reacted to each other just is provided between aggressiveness；
(3) 4.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 280r/min, are warming up to 236 DEG C, copolyreaction 6h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.08MPa is evacuated down to, stops stirring after keeping 0.8h, leads to nitrogen discharging, institute after standing 12min
Reaction product is obtained through Cast Strip pelletizing, Flameproof polyamide 6 is obtained and cuts into slices；
(5) Flameproof polyamide 6 is cut into slices 100 DEG C after extracting 40h, 110 DEG C of vacuum drying 26h, matter is pressed with polyamide 6 section
Measure ratio 1:1.2, which are added to side. by-side conjugation spinning device, carries out melt composite spinning at 285 DEG C, and drafting multiple is 3.2 times, fire-retardant
Polyamide slices and polyamide 6 section obtain side by side after passing sequentially through screw extruder, measuring pump respectively through composite spining module
The composite fibre of type Flameproof polyamide 6 (as shown in Figure 2).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=198, it is the number of repeat unit of polyamide 6；Z=4, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 34.1%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 5.24cN/dtex, elongation at break 30.41%, Young's modulus 32.5cN/dtex.
Embodiment 8
A kind of preparation method of the composite fibre of Flameproof polyamide 6, specifically includes following steps：
(1) fire retardant CEMPP, butanediol are mixed with water, in 60 DEG C of well mixed 3h under nitrogen protection, then 120
Stirring reaction 2h at DEG C, then 170 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation fire retardant pre-polymerization
Body, it is viscous liquid, and number-average molecular weight Mn is 1.8 × 103, fire retardant CEMPP, butanediol and water mol ratio are 1:
1.1:2, obtained flame-retardant agent performed polymer both ends are respectively the active end group of carboxyl and hydroxyl；
The structure of fire retardant is：
(2) 88 mass parts caprolactams, 5.5 mass parts water and 1 mass parts adipic acid are added into reactor, is first passed through N2Row
Go out air in kettle, stirred using rotating speed as 210~r/min and be warming up to 245 DEG C, when pressure reaches 0.5MPa, heat-insulation pressure keeping is anti-
4h is answered, then unloads and is depressed into normal pressure, obtains polyamide 6 performed polymer, the number-average molecular weight Mn of polyamide 6 performed polymer is 6.8 × 103,
And it is respectively the active end group of carboxyl and amido at the both ends of polyamide 6 performed polymer, such polyamide 6 performed polymer and fire retardant
The active end group that can be reacted to each other just is provided between performed polymer；
(3) 5.5 mass parts fire retardant performed polymers are added in polyamide 6 performed polymer, and leads to N into kettle2Protect fire retardant
Performed polymer and polyamide 6 performed polymer are not oxidized, and unlatching speed of agitator is 280r/min, are warming up to 236 DEG C, copolyreaction 6h,
Fire retardant performed polymer is set to be copolymerized with polyamide 6 performed polymer, fire retardant performed polymer can be uniformly dispersed in poly- under high velocity agitation
In the performed polymer of acid amides 6, it can be reacted to each other between the active end group between two performed polymers, strand gradually increases；
(4) then, -0.08MPa is evacuated down to, stops stirring after keeping 0.8h, leads to nitrogen discharging, institute after standing 12min
Reaction product is obtained through Cast Strip pelletizing, Flameproof polyamide 6 is obtained and cuts into slices；
(5) Flameproof polyamide 6 is cut into slices 95 DEG C after extracting 24h, 95 DEG C of vacuum drying 20h, quality is pressed with polypropylene chip
Than 1:1, which is added to core-skin type compined spinning apparatus, carries out melt composite spinning at 274 DEG C, and drafting multiple is 3.7 times, fire-retardant polyamides
Amine 6 is cut into slices and polypropylene chip passes sequentially through obtain core-skin type through composite spining module after screw extruder, measuring pump respectively
The composite fibre of Flameproof polyamide 6 (as shown in Figure 3).The molecular structural formula of the Flameproof polyamide 6 is：
Wherein,
X+y=161, it is the number of repeat unit of polyamide 6；Z=8, it is the number of repeat unit of fire retardant；
For the limited oxygen index of the composite fibre of Flameproof polyamide 6 36.8%, the fracture of the composite fibre of Flameproof polyamide 6 is strong
Spend for 4.51cN/dtex, elongation at break 29.40%, Young's modulus 28.45cN/dtex.
Claims (8)
1. a kind of preparation method of the composite fibre of Flameproof polyamide 6, it is characterized in that：First by fire retardant and diamine or dihydric alcohol
Polycondensation obtains fire retardant performed polymer, is then copolymerized fire retardant performed polymer and the polyamide 6 performed polymer after pre-polymerization,
The material of Flameproof polyamide 6 is obtained, through Cast Strip pelletizing, extraction drying, compined spinning apparatus is added to fibre-forming polymer section and enters
Row melt composite spinning, drawing-off, obtain the composite fibre of Flameproof polyamide 6；The fire retardant performed polymer be viscous liquid or
Semisolid, number-average molecular weight Mn are 103~104, and be the active function groups with carboxyl, amido or hydroxyl at molecule both ends；
The structure of the fire retardant is：
Wherein：The R1For CH, R3For straight chain, branched or ring-type C1~C15Alkylidene；R2、R4For straight chain, branched or ring-type
C1~C15Alkyl or aryl；
The formula of the diamine is H2N-R5-NH2, the formula of dihydric alcohol is HO-R6-OH；R5、R6For the C of straight chain1~C15Asia
Alkyl；
Preparation comprises the following steps that：
(1) fire retardant, diamine or dihydric alcohol are mixed with water, it is well mixed at 50~80 DEG C under nitrogen protection, then 90
Stirring reaction at~130 DEG C, then 150~180 DEG C of further polymerizations are warming up to, last decompression vacuum pumping, reaction terminates generation resistance
Fire agent performed polymer；The mol ratio of the fire retardant, diamine or dihydric alcohol and water is 1:0.8~1.5:2~2.5；
(2) 88~96 mass parts caprolactams, 0.5~5 mass parts water and 0.1~1 mass parts adipic acid are added into reactor, stirred
Mix and be warming up to 245 DEG C~250 DEG C, when pressure reaches 0.5MPa~0.9MPa, heat-insulation pressure keeping reaction a period of time, then unload
Normal pressure is depressed into, obtains polyamide 6 performed polymer；
(3) fire retardant performed polymer described in 2~10 mass parts is added in the polyamide 6 performed polymer, it is 200 to open speed of agitator
~400r/min, 235 DEG C~240 DEG C are warming up to, 6~8h of copolyreaction, fire retardant performed polymer is total to polyamide 6 performed polymer
It is poly-；
(4) then, -0.05~-0.1MPa is evacuated down to, stops stirring after being kept for a period of time, leads to nitrogen after standing 10~20min
Gas discharges, and gained reaction product obtains Flameproof polyamide 6 and cut into slices through Cast Strip pelletizing；
(5) Flameproof polyamide 6 is cut into slices extraction, dry a period of time, cuts into slices with fibre-forming polymer and add by certain mass ratio
Enter to compined spinning apparatus and carry out melt composite spinning, drawing-off, that is, obtain the composite fibre of Flameproof polyamide 6.
A kind of 2. preparation method of the composite fibre of Flameproof polyamide 6 according to claim 1, it is characterised in that step (1)
In, 2~3h, 2~3h of stirring reaction are well mixed, further polymerize 2~3h；In step (2), stir and heat up, rotating speed 200
~400r/min；Heat-insulation pressure keeping reaction a period of time, refer to that heat-insulation pressure keeping reacts 2~4h；In step (4), kept for a period of time
Refer to 0.5~1h of holding.
A kind of 3. preparation method of the composite fibre of Flameproof polyamide 6 according to claim 1, it is characterised in that step (2)
It is middle to stir and need first to be passed through N before heating up2Air in kettle is discharged, when fire retardant performed polymer is added in reactor in step (3)
Need to lead to N into kettle2Protect fire retardant performed polymer and polyamide 6 performed polymer not oxidized.
A kind of 4. preparation method of the composite fibre of Flameproof polyamide 6 according to claim 1, it is characterised in that step (5)
The extraction that middle Flameproof polyamide 6 is cut into slices refers to that 24~48h of extraction, the drying of section refer at 90~110 DEG C at 95~100 DEG C
12~48h of lower vacuum drying；The melt composite spinning temperature that Flameproof polyamide 6 is cut into slices in step (5) is 265~285 DEG C, drawing-off
Multiple is 3.2~3.8；It is 1 that Flameproof polyamide 6, which is cut into slices with the mass ratio of fibre-forming polymer section,:0.8~1.2.
A kind of 5. preparation method of the composite fibre of Flameproof polyamide 6 according to claim 1, it is characterised in that it is described into
Fine polymer is polyamide, polyester or polypropylene.
A kind of 6. preparation method of the composite fibre of Flameproof polyamide 6 according to claim 1, it is characterised in that step (5)
In the obtained composite fibre of Flameproof polyamide 6 be parallel type, core-skin type, exfoliated or fabric of island-in-sea type.
7. a kind of composite fibre of Flameproof polyamide 6 made from the preparation method as described in any one of claim 1~6 is used, its
It is characterized in：It is formed by Flameproof polyamide 6 and fibre-forming polymer melt composite spinning, the molecular structure of the Flameproof polyamide 6
Formula is：
Wherein,
X >=50, y >=50；z≥2；And 1/100≤z/ (x+y)≤1/10；
R is
The R1For CH, R3For straight chain, branched or ring-type C1~C15Alkylidene；R2、R4For straight chain, branched or ring-type C1~
C15Alkyl or aryl；R5、R6For the C of straight chain1~C15Alkylidene；
More than 30%, the composite fibre of Flameproof polyamide 6 breaks the limited oxygen index of the composite fibre of Flameproof polyamide 6
Resistance to spalling is 4.0~6.7cN/dtex, and elongation at break is 22~38%, and Young's modulus is 20~37cN/dtex.
8. the composite fibre of a kind of Flameproof polyamide 6 according to claim 7, it is characterised in that the fibre-forming polymer is
Polyamide, polyester or polypropylene.
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| CN106675007B (en) * | 2017-01-06 | 2019-08-09 | 东华大学 | A kind of Flameproof polyamide 6 and preparation method thereof |
| CN107447282B (en) * | 2017-08-17 | 2020-02-14 | 中央军委后勤保障部军需装备研究所 | Antibacterial flame-retardant polyamide 66 and preparation method thereof |
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| CN109705341B (en) * | 2019-01-10 | 2021-04-16 | 军事科学院系统工程研究院军需工程技术研究所 | P-N-Si synergistic flame-retardant copolymerized polyamide 66 and preparation method thereof |
| CN110079879A (en) * | 2019-04-29 | 2019-08-02 | 吴江精美峰实业有限公司 | A kind of sea-island fibre and the method and composite spining module for being used to prepare sea-island fibre |
| CN111234157B (en) * | 2020-03-09 | 2021-10-19 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
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